Photoinduced Trifluoromethylation of Arenes and Heteroarenes Catalyzed by High‐Valent Nickel Complexes

Abstract

AbstractWe describe a series of air‐stable NiIII complexes supported by a simple, robust naphthyridine‐based ligand. Access to the high‐valent oxidation state is enabled by the CF3 ligands on the nickel, while the naphthyridine exhibits either a monodentate or bidentate coordination mode that depends on the oxidation state and sterics, and enables facile aerobic oxidation of NiII to NiIII. These NiIII complexes act as efficient catalysts for photoinduced C(sp2)−H bond trifluoromethylation reactions of (hetero)arenes using versatile synthetic protocols. This blue LED light‐mediated catalytic protocol proceeds via a radical pathway and demonstrates potential in the late‐stage functionalization of drug analogs.